Fluorocopolymers for coating applications

ABSTRACT

Disclosed are copolymers formed by copolymerization of: (1) one or more hydrofluoroolefin monomer(s) selected from the group consisting of hydrofluoroethylenes, hydrofluoropropenes, hydrofluorobutenes, hydrofluoropentenes and combinations of these, and preferably selected from 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, with said 1,3,3,3-tetrafluoropropene preferably comprising, consisting essentially of or consisting of trans-1,3,3,3-tetrafluoropropene, and combinations of these, and (2) one or more chlorofluoroethylene monomers, preferably chlorotrifluoroethylene (“CTFE”) monomers, wherein the mole ratio of monomer (1) to monomer (2) is preferably from about 30:1 to about 1:30.

RELATED APPLICATIONS

This application claims the benefit of U.S. provisional application Ser.No. 62/257,812, filed Nov. 20, 2015, which is incorporated herein byreference in its entirety.

FIELD OF THE INVENTION

The present invention relates to novel fluorocopolymers having excellentadhesion to substrates and excellent resistance to weathering andcorrosion, as well as other advantageous properties, and coatingcompositions formed from such polymers having high solids content, andto methods of reducing the exposure of earth's atmosphere to volatileorganic compounds (VOCs) while forming protective coatings onsubstrates.

BACKGROUND OF THE INVENTION

Volatile organic compounds (VOCs) are volatile compounds of carbon thatare subject to regulation by various government authorities, and for thepurposes of the present invention the term is used consistent withproposed regulations established by the United States EnvironmentalProtection Agency (EPA). More specifically, these proposed regulationsestablish that a compound of carbon is a VOC if it has a vapor pressureof less than about 0.1 millimeters of mercury at 20° C.

A variety of chemicals are within the definition of VOC, and some ofthese chemicals have short- and long-term adverse health effects whenreleased into the atmosphere. Accordingly, many countries haveregulations governing the release of such compounds into the earth'satmosphere. One relatively large source of release of such compoundsinto the environment has been from the solvents that are used in coatingproducts such as, paints, varnishes, waxes, adhesives, inks and thelike. Many cleaning, disinfecting, cosmetic, degreasing, and hobbyproducts also contain VOCs as solvents or carriers. One method to reduceor eliminate the release of such compounds into the atmosphere is tocapture and prevent release of the solvent as it evaporates from thecoating composition. Such methods can involve, for example, theinstallation of a mechanism to capture the vapors and to process suchvapors in an incinerator. However, as will be appreciated to thoseskilled in the art a substantial capital cost and/or processing cost isincurred as a result of such operations, and such operations cansometimes add detrimentally to the time required to complete suchcoating operations.

In order to reduce and control the VOC emission into the earth'satmosphere, more and more countries have started to regulate VOCemissions. Such regulations include in various countries charging a VOCtax upon release of such compounds. Accordingly, there are manyincentives to reduce the release of VOCs into the atmosphere.

SUMMARY OF THE INVENTION

One aspect of the present invention provides fluorocopolymers formed bycopolymerization of:

-   -   (1) one or more hydrofluoroolefin monomer(s) selected from the        group consisting of hydrofluoroethylenes, hydrofluoropropenes,        hydrofluorobutenes, hydrofluoropentenes and combinations of        these, and preferably selected from 2,3,3,3-tetrafluoropropene,        1,3,3,3-tetrafluoropropene, with said 1,3,3,3-tetrafluoropropene        preferably comprising, consisting essentially of or consisting        of trans-1,3,3,3-tetrafluoropropene, and combinations of these,        and    -   (2) one or more chlorofluoroethylene monomers, preferably        chlorotrifluoroethylene (“CTFE”) monomers, wherein the mole        ratio of monomer (1) to monomer (2) is preferably from about        30:1 to about 1:30.

As used herein, the term “copolymer” means polymers having two or moredifferent repeating units, and the term “fluorocopolymer” meanscopolymers in which at least one of the repeating units is based on amonomer that is a hydrofluoroolefin. The term “terpolymer” meanspolymers having three or more different repeating units, and the term“terfluorocopolymer” means terpolymers in which at least one of therepeating units is based on a monomer that is a hydrofluoroolefin. Theterm “tetrapolymer” is intended to include oligomers and copolymershaving four or more different repeating units, and the term“tetrafluorocopolymer” means tetrapolymers in which at least one of therepeating units is based on a monomer that is a hydrofluoroolefin. Thus,a tetrapolymer derived from monomers A, B, C and D has repeating units(-A-), (—B—), (—C—) and (-D-), and a tetrafluorocopolymer derived frommonomers A, B, C and D wherein at least one of these is ahydrofluoroolefin.

The repeating units according to the present invention can be arrangedin any form, including as alternating copolymers, as periodiccopolymers, statistical copolymers, block copolymers and graftcopolymers.

According to certain preferred embodiments, the present inventionprovides terfluorocopolymers, and preferably tetrafluorcopolymers,formed by copolymerization of:

-   -   (1) one or more hydrofluoroolefin monomer(s) selected from the        group consisting of hydrofluoroethylenes, hydrofluoropropenes,        hydrofluorobutenes, hydrofluoropentenes and combinations of        these, and preferably selected from 2,3,3,3-tetrafluoropropene,        1,3,3,3-tetrafluoropropene, with said 1,3,3,3-tetrafluoropropene        preferably comprising, consisting essentially of or consisting        of trans-1,3,3,3-tetrafluoropropene, and combinations of these;    -   (2) one or more chlorofluoroethylene monomers, preferably        chlorotrifluoroethylene (“CTFE”) monomers;    -   (3) optionally but preferably one or more vinyl ester        monomer(s); and    -   (4) one or more vinyl ether monomer(s), wherein at least a        portion of said vinyl ether monomer is a hydroxyl        group-containing vinyl ether monomer.

According to preferred aspects, the present invention providestetrafluorocopolymers as described in the previous paragraph wherein thepolymer has a number average molecular weight of greater than about10,000, preferably greater than about 12,000, and preferably in otherembodiments greater than about 15,000.

One aspect of the present invention provides methods of reducing therelease of volatile organic compounds (VOCs) into the earth's atmosphereduring coating operations of the type that permit the escape of VOCsinto the earth's atmosphere. In preferred embodiments the methodsaccording to this aspect include the steps of:

-   -   (a) providing a substrate to be coated;    -   (b) providing a coating composition which is formed by steps        comprising:        -   (i) providing one or more fluorocopolymers by            copolymerization of (1) one or more hydrofluoroolefin            monomer(s) selected from the group consisting of            hydrofluoroethylenes, hydrofluoropropenes,            hydrofluorobutenes, hydrofluoropentenes and combinations of            these, and preferably selected from            2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, with            said 1,3,3,3-tetrafluoropropene preferably comprising,            consisting essentially of or consisting of            trans-1,3,3,3-tetrafluoropropene, and combinations of            these, (2) one or more chlorofluoroethylene monomers,            preferably chlorotrifluoroethylene (“CTFE”) monomers, (3)            one or more vinyl ester monomer(s), and (4) one or more            vinyl ether monomer(s), wherein at least a portion of said            vinyl ether monomer is a hydroxyl group-containing vinyl            ether monomer, wherein the copolymer preferably has a number            average molecular weight of greater than about 10,000,            preferably greater than about 12,000, and certain other            embodiments greater than about 15,000, as measured according            the procedure as described herein; and        -   (ii) providing a carrier for said one or more            fluorocopolymers, said carrier comprising one or more VOC            compounds; and        -   (iii) combining said one or more fluorocopolymers with said            carrier to produce a polymeric composition comprising not            greater than about 30% by weight of said carrier, preferably            with a solids content of at least about 70% by weight;    -   (c) coating the substrate with said coating composition; and    -   (d) forming a protective polymeric layer on said substrate by        allowing at least a substantial portion of said VOCs in said        carrier to evaporate into the earth's atmosphere, whereby said        protective coating is formed.

Another aspect of the present invention provides methods for obtaining aVOC tax credit as a result of reducing the release of volatile organiccompounds (VOCs) into the earth's atmosphere compared to a baselinecoating operation of the type that permits the escape of VOCs into theearth's atmosphere. In preferred embodiments, methods according to thisaspect include the steps of:

-   -   (a) establishing a baseline release of VOCs from an existing        operation which involves coating of a substrate with an existing        coating composition;    -   (b) providing a reduced VOC coating composition formed by steps        comprising:        -   (i) providing one or more fluoropolymers by copolymerization            of (1) one or more hydrofluoroolefin monomer(s) selected            from the group consisting of hydrofluoroethylenes,            hydrofluoropropenes, hydrofluorobutenes, hydrofluoropentenes            and combinations of these, and preferably selected from            2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, with            said 1,3,3,3-tetrafluoropropene preferably comprising,            consisting essentially of or consisting of            trans-1,3,3,3-tetrafluoropropene, and combinations of            these, (2) one or more chlorofluoroethylene monomers,            preferably chlorotrifluoroethylene (“CTFE”) monomers, (3)            one or more vinyl ester monomer(s), and (4) one or more            vinyl ether monomer(s), wherein at least a portion of said            vinyl ether monomer is a hydroxyl group-containing vinyl            ether monomer, wherein the copolymer preferably has a number            average molecular weight of greater than about 10,000,            preferably greater than about 12,000 and certain other            embodiments greater than about 15,000, as measured according            the procedure as described herein; and        -   (ii) providing a carrier for said one or more            fluoropolymers, said carrier comprising one or more VOC            compounds; and        -   (iii) combining said one or more fluoropolymers with said            carrier to produce a polymeric composition comprising not            greater than about 30% by weight of said carrier, preferably            with a solids content of at least about 70% by weight;    -   (c) coating the substrate with said reduced VOC coating        composition; and    -   (d) forming a protective polymeric layer on said substrate by        allowing at least a substantial portion of said VOCs in said        carrier to evaporate into the earth's atmosphere, whereby said        protective coating is formed and whereby the VOCs released using        said reduced VOC coating compositions is reduced compared to        said baseline release of VOC; and    -   (e) submitting to an appropriate governmental agency a claim for        tax credit based at least in part on said reduction in VOCs        released from said coating operation.

According to certain preferred embodiments, the fluorocopolymer coatingcomposition formed by step (b) of this invention has a solid content offrom about 70% to about 90% by weight, and even more preferably incertain embodiments from about 75% to about 85% by weight. In preferredembodiments the fluorocopolymer coating composition formed by step (b)of this invention has a solid content of greater than about 75%

According to preferred embodiments, the fluorocopolymer coatingcomposition formed by step (b) of this invention has a VOC content ofless than about 450 g/l, more preferably less than about 400 g/l, andeven more preferably less than about 350 g/l.

According to preferred embodiments, the fluorocopolymer coatingcomposition formed by step (b) of this invention has a VOC content offrom about 450 g/l to about 100 g/l, more preferably from about 400 g/lto about 200 g/l, and even more preferably from about 350 g/l to about250 g/l.

As used herein, the term hydrofluoroolefins means compounds consistingof carbon, hydrogen and fluorine and having at least one carbon-carbondouble bond. Hydrofluoroolefins include, but are not necessarily limitedto, hydrofluoroethylenes, hydrofluoropropenes, hydrofluorobutenes andhydrofluoropentenes, and the like. Preferred hydrofluoroolefins used toform the coating composition of step (b) comprise one or moretetrafluoropropenes. The tetrafluoropropene(s) used in step (b)preferably comprise 1,3,3,3-tetrafluoropropene (HFO-1234ze) and/or2,3,3,3-tetrafluoropropene (HFO-1234yf), with said1,3,3,3-tetrafluoropropene preferably comprising, consisting essentiallyof or consisting of trans-1,3,3,3-tetrafluoropropene.

As used herein, the term chlorofluoroethylene means compounds consistingof 2 carbon atoms having a carbon-carbon double bond, chlorine andfluorine, and includes but is not necessarily limited tochlorotrifluoroethylene.

In preferred embodiments, the fluoropolymer of step (b) is formed bysolution copolymerization of the monomers represented by (1), (2), (3)and (4) of step (b) (i). In preferred embodiments, step (b)(i) comprisessolution copolymerizing:

(1) from about 40 mol % to about 60 mol %, and even more preferably fromabout 45 mol % to about 55 mol %, and even more preferably about 50 mol% of hydrofluoroolefin monomer(s), preferably selected from the groupconsisting of hydrofluoroethylenes, hydrofluoropropenes,hydrofluorobutenes and hydrofluoropentenes, more preferably from thegroup consisting of HFO-1234ze, HFO-1234yf and combinations of these,and even more preferably HFO-1234ze, with said HFO-1234ze preferablycomprising, consisting essentially of or consisting of trans-HFO-1234ze;

(2) from about 40 mol % to about 60 mol %, and even more preferably fromabout 45 mol % to about 55 mol %, and even more preferably about 50 mol% of chlorofluoroethylene monomer(s), preferably CTFE, wherein the moleratio of monomer (1) to monomer (2) is preferably from about 30:1 toabout 1:30;

(3) from about 5 mol % to 45 mol % of vinyl ester or vinyl either orboth of them, more preferably from about 10 mol % to about 40 mol %, andeven more preferably from about 20 mol % to about 40 mol %, representedby formula CH₂═CR¹—O(C═O)_(X)R² and CH₂═CR³—OR⁴ respectively, wherein xis 1 and wherein Wand R³ are independently either hydrogen or a methylgroup, preferably hydrogen, and wherein R² and R⁴ are independentlyselected from the group consisting of an unsubstituted straight-chain,branched-chain or alicyclic alkyl group having 1 to 12 carbon atoms,preferably from 2 to 8 carbon atoms; and

(4) from about 3 mol % to about 30 mol % of hydroxyalkyl vinyl ether,more preferably from about 3 mol % to about 20 mol %, and even morepreferably from about 3 mol % to about 10 mol % represented by formulaCH₂═CR³—O—R⁵—OH, where R³ is as defined above, preferably hydrogen, andR⁵ is selected from the group consisting of a C2 to C12 unsubstitutedstraight-chain, branched-chain or alicyclic alkyl group, more preferablyan unsubstituted straight chain alkyl group having from 3 to 5 carbons,preferably 4 carbons, wherein the mol % are based on the total of themonomers in the copolymer formation step.

According to preferred embodiments, the fluorocopolymer coatingcomposition formed by step (b) of this invention has a VOC content offrom about 450 g/l to about 100 g/l, more preferably from about 400 g/lto about 200 g/l, and even more preferably from about 350 g/l to about250 g/l.

As used herein, the term hydrofluoroolefins includes but is notnecessarily limited to hydrofluoroethylene, hydrofluoropropene,hydrofluorobutene and hydrofluoropentene, and the like. According tocertain preferred embodiments, the hydrofluoroolefin used to form thecoating composition of step (b) comprises 1,3,3,3-tetrafluoropropene(HFO-1234ze) and/or 2,3,3,3-tetrafluoropropene (HFO-1234yf), with saidHFO-1234ze preferably comprising, consisting essentially of orconsisting of trans-HFO-1234ze.

In preferred embodiments, the fluorocopolymer of step (bi) is formed bycopolymerization, and preferably solution copolymerization, of themonomers represented by (1), (2), (3) and (4) as follows:

(1) from about 40 mol % to about 60 mol %, and even more preferably fromabout 45 mol % to about 55 mol %, and even more preferably about 50 mol% of hydrofluoroolefin monomers, preferably selected from the groupconsisting of hydrofluoroethylenes, hydrofluoropropenes,hydrofluorobutenes and hydrofluoropentenes, preferably from the groupconsisting of HFO-1234ze, HFO-1234yf and combinations of these, and evenmore preferably HFO-1234ze with said HFO-1234ze preferably comprising,consisting essentially of or consisting of trans-HFO-1234ze;

(2) from about 40 mol % to about 60 mol %, and even more preferably fromabout 45 mol % to about 55 mol %, and even more preferably about 50 mol% of chlorofluoroethylene monomer(s), preferably CTFE, wherein the moleratio of monomer (1) to monomer (2) is from about 30:1 to about 1:30,

(3A) from about 10 mol % to about 40 mol % of vinyl ester, morepreferably from about 10 mol % to about 30 mol %, and even morepreferably from about 10 mol % to about 20 mol %, represented by formulaCH₂═CR¹—O(C═O)_(X)R², wherein x is 1 and wherein R¹ is either hydrogenor a methyl group, and wherein R² is selected from the group consistingof an unsubstituted straight-chain, branched-chain or alicyclic alkylgroup having 1 to 12 carbon atoms;

(3B) from about 10 mol % to about 40 mol % of vinyl ether, morepreferably from about 10 mol % to about 30 mol %, and even morepreferably from about 10 mol % to about 20 mol %, represented by formulaCH₂═CR³—OR⁴ respectively, wherein R³ is independently either hydrogen ora methyl group and wherein R⁴ are independently selected from the groupconsisting of an unsubstituted straight-chain, branched-chain oralicyclic alkyl group having 1 to 12 carbon atoms; and

(4) from about 3 mol % to about 30 mol % of hydroxyalkyl vinyl ether,more preferably from about 3 mol % to about 20 mol %, and even morepreferably from about 3 mol % to about 10 mol % represented by formulaCH₂═CR³—O—R⁵—OH, where R³ is as defined above, preferably hydrogen, andR⁵ is selected from the group consisting of a C2 to C12 unsubstitutedstraight-chain, branched-chain or alicyclic alkyl group, wherein the mol% are based on the total of the monomers in the copolymer formationstep.

In preferred embodiments, the fluoropolymer coating composition formedby step (b) of the present invention has a solids content of from about70% to about 90% by weight, more preferably in certain embodiments offrom about 75% to about 85% by weight, and at the same time has a VOCcontent of from about 450 g/l to about 100 g/l, more preferably fromabout 400 g/l to about 200 g/1, and even more preferably from about 300g/l to about 200 g/l.

According to a preferred embodiment of the present invention, theco-polymer formation step (b) (i) comprises providing one or morefluorocopolymers by copolymerization of:

-   -   (1) first monomer(s) consisting essentially of HFO-1234ze and/or        HFO-1234yf, wherein the HFO-1234ze is preferably        trans-HFO-1234ze, preferably in an amount of from about 5 mol %        to about 60 mol %, and more preferably from about 10 mol % to        about 55 mol %,    -   (2) second monomer comprising CTFE, preferably in an amount of        from about 5 mol % to about 60 mol %, and more preferably from        about 10 mol % to about 55 mol %, wherein the mole ratio of        monomer (1) to monomer (2) is from about 5:1 to about 1:5, more        preferably from about 2:1 to about 1:2;    -   (3) third monomer(s) comprising:        -   A) vinyl ester monomer(s), preferably in an amount of from            about 5 mol % to about 45 mol %, more preferably from about            10 mol % to about 30 mol %, and even more preferably from            about 10 mol % to about 20 mol %, represented by formula            CH₂═CR¹—O(C═O)_(X)R², wherein x is 1 and wherein R¹ is            either hydrogen or a methyl group, and wherein R² is            selected from the group consisting of a substituted or            unsubstituted straight-chain or branched-chain alkyl group            having 5 to 12 carbon atoms, wherein said alkyl group            includes at least one tertiary or quaternary carbon atom,            and        -   B) vinyl ether monomer(s), preferably in amounts of from            about 10 mol % to about 40 mol % of vinyl ether, more            preferably from about 5 mol % to about 45 mol %, more            preferably from about 10 mol % to about 30 mol %, and even            more preferably from about 10 mol % to about 20 mol %,            represented by formula CH₂═CR³—OR⁴ respectively, wherein R³            is independently either hydrogen or a methyl group and            wherein R⁴ is independently selected from the group            consisting of a substituted or unsubstituted straight-chain            or branched-chain alkyl group having 1 to 5 carbon atoms;            and    -   (4) fourth monomer(s) selected from hydroxyl group-containing        vinyl ether monomer(s), preferably in an amount of from about 3        mol % to about 60 mol % of hydroxy vinyl ether monomer,        preferably in an amount of from about 3 mol % to about 30 mol %,        more preferably from about 3 mol % to about 20 mol %, and even        more preferably from about 3 mol % to about 10 mol %,        represented by formula CH₂═C—R⁵—OH, where R⁵ is selected from        the group consisting of a C2 to C6 substituted or unsubstituted        straight-chain or branched-chain alkyl group, wherein the mol %        are based on the total of the monomers in the copolymer        formation step.

As used herein, unless otherwise specifically indicated, reference tomol % is to the mol % of monomers used in the formation of thefluorocopolymer of the present invention, based on the total of themonomers.

In certain embodiments of the process, the copolymer formed by step (b)of the present invention has a number average molecular weight asmeasured by gel phase chromatography (“GPC”) according to the methoddescribed in Skoog, D. A. Principles of Instrumental Analysis, 6th ed.;Thompson Brooks/Cole: Belmont, Calif., 2006, Chapter 28, which isincorporated herein by reference, of from about 5000 and 50,000, morepreferably from about 12,000 to about 20,000 and in certain embodimentsa weight average molecular weight preferably from about 5000 to about30,000, and more preferably from about 20,000 to about 30,000. Thevalues described herein for molecular weight are based on measurementsthat use an Agilent-PL gel chromatography column (5 um MIXED-C 300*7.5mm). The mobile phase is tetrahydrofuran (THF) at a flow rate of 1ml/minute and a temperature of 35° C. A refractive index detector isused. The unit is calibrated with polystyrene narrow standard availablefrom Agilent.

In certain embodiments, the coating composition formed by step (b) has aVOC content of less than about 450 g/1, more preferably less than about400 g/l, and even more preferably less than about 300 g/l. The valuesdescribed herein for VOC are based on measurements made according toASTM 22369.9963 which covers the standard test method for thedetermination of the weight percent volatile content of solvent-borneand water-borne coatings. The procedure for calculating the VolatileOrganic Compound (VOC) content of a liquid coating is to obtain a sampleof the liquid coating to be tested and then weighing the coating in analuminum foil dish to obtain the weight to the nearest 0.1 mg, which isdesignated in the following calculations as (W1). Add to the aluminumfoil dish 3±1 ml of toluene solvent to form the coating specimen. Thespecimen is then draw into the syringe and the filled syringe is placedon the scale and the scale is tarred. The cap is removed from thesyringe and the specimen is dispensed from the syringe into the dish tothe target specimen weight (0.3±0.1 g if the expected result is =<40%volatile and 0.5±0.1 g if the expected result is =>40% volatile. Thespecimen is spread out in the dish to cover the bottom of the dishcompletely with as uniform thickness as possible. Obtain and record theweight of the specimen to the nearest 0.1 mg, which is designated as theSpecimen Weight (SA) in the following calculations. The foil dishcontaining the specimens is then heated in the forced draft oven for 60min at 110° C. Each dish is removed from the oven, placed immediately ina desiccator, cooled to ambient temperature, weighed to the nearest 0.1mg, and this weigh is record, and is indicated as W2 in the followingcalculations.

To calculate the VOC, V, in the liquid coating, the following equationsare used:VA=1000*DA*(W2−W1)/SA]

Where:

VA=% volatiles (first determination),

W1=weight of dish,

W2=weight of dish plus specimen

SA=specimen weight,

DA=specimen specific Gravity and

VB=% volatiles (duplicate determination; calculate in same manner asVA).

As used herein, the term “substrate” refers to any device or article, orpart of a device or article, to be coated.

As used herein, the term “carrier” is intended to refer to a componentof a composition that serves to solvate, disperse and/or emulsify amonomeric or polymeric component of a composition.

DETAILED DESCRIPTION OF THE INVENTION

As described above, preferred aspects of the present invention involvecoating methods that provide reduced VOC emissions while at the sametime providing effective and efficient protective coatings onsubstrates. As those skilled in the art will appreciate, the quality ofa protective coating applied to a substrate can be measured by a varietyof coating properties that, depending on the particular application, areimportant for achieving a commercially successful coating on a givensubstrate. These properties include but are not limited to: (1)viscosity, (2) color retention and (3) substrate adhesion.

Viscosity as used herein is measured according the ASTM Standard TestMethod for Measuring Solution Viscosity of Polymers with DifferentialViscometer, Designation D5225-14. According to this method as usedherein, the viscometer used is a Brookfield viscometer (DV-II+Pro) usingspindles S18/S31 using torque values from between 40% and 80% at roomtemperatures of about 23±2° C. If a solvent is used for themeasurements, it is butyl acetate.

According to certain preferred embodiments, the coating compositionsformed according to the present methods exhibit: (1) a solidconcentration of at least about 70% by weight; (2) a viscosity, asmeasured by the ASTM Standard Test Method for Measuring SolutionViscosity of Polymers with Differential Viscometer, DesignationD5225-14, of not greater than about 1700 mPa-s at about 23±2° C., and acolor change after about 1000 hours, of not greater than 2.0, morepreferably not greater than about 1.5, and even more preferably notgreater than about 1.2, as measured in comparison to the initial color,each as measured by ASTM D 7251, QUV-A; and a VOC content of not greaterthan about 450 g/l, more preferably not greater than about 400 g/l, andeven more preferably not greater than about 350 g/l.

The QUV-A is measured as indicated above according to ASTM D 7251, whichis QUV Accelerated Weathering Tester Operating Procedure by whichaccelerated testing is performed in an accelerated testing cabinet soldunder the trade mark QUV® manufactured by Q-Lab Corporation of ClevelandOhio. Two lamps are used in this testing cabinet: “A” lamps (UVA-340)have a normal output of 0.69 W/m² @ 340 nm m and a maximum output of1.38 W/m² @ 340 nm m; and “B” lamps (UVA-313) have a normal output of0.67 W/m² @ 310 nm 0.67 and a maximum output of 1.23 W/m² @ 310 nm m. Asused herein, the designation QUV-A refers to tests using the A lamps andQUA-B refers to tests using the B lamps. The procedure is accomplishedusing the following steps:

-   -   1. Measure the initial gloss of the coating film three times and        obtain the average of the measurements, which is designated in        the following calculations as “A.”    -   2. Place the test plate containing the coating in the panel        holder in the cabinet and power the cabinet on.    -   3. Set the PROGRAM button in the control panel and select the        desired program operation.    -   4. Engage the RUN button to start test.    -   5. Record down the exposure time indicated on the led panel    -   6. Stop the machine after the indicated hours, remove the test        plate, and measure the gloss three times to get an average        result for the indicated exposure time, and record this value as        “B” for use in the calculation below.    -   7. Determine Gloss retention using the formula Gloss        Retention=B/A

In preferred embodiments, the polymers of the present invention have ahydroxyl value of greater than about 70, and in other preferredembodiments have a hydroxyl value of greater than about 90. As mentionedabove, the ability to achieve such a method resides, in part, on thejudicious selection of the type and the amounts of the variouscomponents that are used to form the fluoropolymer and the coatingcompositions of the present invention.

In preferred embodiments, the polymers of the present invention have afluorine content of from about 15% to about 20% by weight and a chlorinecontent of from about 12% to about 18% by weight. In other preferredembodiments, the polymers of the present invention have fluorine contentof from about 16% to about 18% by weight and a chlorine content of fromabout 14% to about 16% by weight.

Monomers

Hydrofluoroolefins

The hydrofluoroolefin monomers according to the methods of the presentinvention can include in certain preferred embodimentshydrofluoroethylene monomer, that is, compounds having the formulaCX¹X²═CX³X⁴; wherein X′, X², X³, X⁴ are each independently selected fromH or F or Cl atom, but at least one of them is a hydrogen atom. Examplesof hydrofluoroethylene monomers include, among others:

CH₂═CHF,

CHF═CHF,

CH₂═CF₂, and

CHF═CF₂.

The hydrofluoroolefin monomers according to certain preferred aspects ofthe methods of the present invention include, and preferably consistsessentially of or consist of hydrofluoropropenes having the formulaCX⁵X⁶═CX⁷CX⁸X⁹X¹⁹; wherein X⁵, X⁶, X⁷, X⁸, X⁹ and X¹⁰ are independentlyselected from H or F or Cl atom, but at least one of them is a hydrogenatom and another is a fluorine atom. Examples of hydrofluoro-propenemonomers include, among others:

-   -   CH₂═CFCF₃ (HFO-1234yf),    -   trans-CHF═CHCF₃ (trans-HFO-1234ze),    -   CHCl═CFCF₃ and    -   CH₂═CHCF₃.

In preferred embodiments, the hydrofluoroolefin comprises, consistsessentially of or consist of HFO-1234yf and/or HFO-1234ze. In preferredembodiments, the hydrofluoroolefin comprises, consists essentially of orconsist of HFO-1234ze, with said HFO-1234ze preferably comprising,consisting essentially of or consisting of trans-HFO-1234ze.

The hydrofluoroolefin monomers according to certain preferred aspects ofthe methods of the present invention include, hydrofluorobuteneaccording to the following formula: CX¹¹X¹²═CX¹³CX¹⁴X¹⁵CX¹⁶X¹⁷X¹⁸;wherein X¹¹, X¹², X¹³, X¹⁴, X¹⁵, X¹⁶, X¹⁷ and X^(is) are independentlyselected from H or F or Cl atom, but at least one of them is a hydrogenatom and at least one is a fluorine atom. Examples of hydrofluorobuteneinclude, among others, CF₃CH═CHCF₃.

Vinyl Esters

The copolymers in accordance with the present invention preferably arealso formed from vinyl ester monomer units, preferably in amounts offrom about 5 mol % to about 45 mol %, more preferably from about 10 mol% to about 30 mol %, and even more preferably from about 10 mol % toabout 20 mol %. In preferred embodiments the vinyl ester monomer(s) arerepresented by the formula CH₂═CR¹—O(C═O)_(X)R², wherein x is 1 andwherein R¹ is either hydrogen or a methyl group, and wherein R² isselected from the group consisting of a substituted or unsubstituted,preferably unsubstituted, straight-chain or branched-chain, preferablybranched chain, alkyl group having 5 to 12 carbon atoms, more preferablyhaving from 5 to 10 carbon atoms, and even more preferably 8 to 10carbon atoms. In preferred embodiments the alkyl group includes at leastone tertiary or quaternary carbon atom. In highly preferred embodiments,the vinyl ester includes at least one quaternary carbon according to thefollowing formula:

where each of R⁷ and R⁸ are alkyl groups, preferably branched alkylgroups, that together contain from 5 to about 8, more preferably from 6to 7, carbon atoms.

Examples of vinyl ester monomers that are preferred according to certainpreferred embodiments include vinyl acetate, vinyl propionate, vinylbutyrate, vinyl pivalate, vinyl capronate, vinyl laurate, VEOVA-9 (vinylversatate ester formed from a C9 carbocylic acid, produced byMomentive), VEOVA-10 (vinyl versatate ester formed from a C10carbocyclic acid, produced by Momentive) and vinylcyclohexanecarboxylate. Each of VEOVA-9 and VEOVA-10 contain at leastone quaternary carbon according to Formula A above. According topreferred embodiments, the vinyl ester comprises vinyl versatate esterhaving from 11 to 12 carbon atoms in the molecule, preferably with atleast one quaternary carbon according to Formula A above.

Vinyl Ethers

The copolymers in accordance with the present invention preferably arealso formed from vinyl ether monomer units, preferably in amounts offrom about 5 mol % to about 45 mol %, more preferably from about 10 mol% to about 30 mol %, and even more preferably from about 10 mol % toabout 20 mol %. In preferred embodiments the vinyl ester monomer(s) arerepresented by the formula CH₂═CR³—OR⁴, wherein R³ is independentlyeither hydrogen or a methyl group and wherein R⁴ is selected from thegroup consisting of a substituted or unsubstituted, preferablyunsubstituted, straight-chain or branched-chain, preferably straightchain, alkyl group having 1 to 5 carbon atoms, more preferably 1 to 3carbon atoms. Examples of vinyl ether monomers that are preferredaccording to certain preferred embodiments include alkyl vinyl etherssuch as methyl vinyl ether, ethyl, propyl vinyl ether, n-butyl vinylether, isobutyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decylvinyl ether and lauryl vinyl ether. Vinyl ethers including an alicyclicgroup can also be used, for example, cyclobutyl vinyl ether, cyclopentylvinyl ether and cyclohexyl vinyl ether. According to preferredembodiments the vinyl ether comprises, consists essentially of, orconsists of ethyl vinyl ether.

Preferably in those embodiments in which vinyl ether and vinyl estermonomers are both present, the amount of vinyl ether and vinyl estermonomers together comprise from about 25 mol % to about 45 mol % of thetotal monomers.

Hydroxy Vinyl Ethers

The copolymers in accordance with the present invention preferably arealso formed from hydroxyl vinyl ether monomer units, preferably inamounts of from about 3 mol % to about 60 mol % of hydroxy vinyl ethermonomer, preferably in an amount of from about 3 mol % to about 30 mol%, more preferably from about 3 mol % to about 20 mol %, and even morepreferably from about 3 mol % to about 10 mol %. In preferredembodiments the hydroxyl vinyl ether monomer(s) are represented by theformula represented by formula CH₂═CR³—O—R⁵—OH, where R³ is as definedabove, preferably hydrogen, and where R⁵ is selected from the groupconsisting of a C2 to C6 substituted or unsubstituted, preferablyunsubstituted, straight-chain or branched-chain, prefeethrably straightchain, alkyl group. Examples of preferred hydroxyalkyl vinyl ethermonomers include hydroxyl-ethyl vinyl ether, hydroxypropyl vinyl ether,hydroxybutyl vinyl ether, hydroxypentyl vinyl ether and hydroxyhexylvinyl ether. In certain embodiments, the copolymer is formed from about5 mol % to about 20 mol % of hydroxyalkyl vinyl ether monomers, based onthe total weight of the monomer.

In preferred embodiments, the co-monomers according to thefluorocopolymer formation step (b)(i) comprise, and preferably consistessentially of:

(1) first monomer consisting essentially of HFO-1234ze, preferably in anamount of from about 20 mol % to about 30 mol %, and even morepreferably from about 22 mol % to about 27 mol %, and even morepreferably about 25 mol %,

(1) second monomer consisting essentially of CTFE, preferably in anamount of from about 20 mol % to about 30 mol %, and even morepreferably from about 22 mol % to about 27 mol %, and even morepreferably about 25 mol %,

(3) third monomer(s) comprising:

-   -   A) vinyl ester monomer represented by formula        CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is either        hydrogen or a methyl group, preferably hydrogen, and wherein R²        is a substituted or unsubstituted branched or branched-chain        alkyl group having 6 to 8 carbon atoms, preferably an        unsubstituted branched-chain alkyl group having 6 to 8 carbon        atoms, wherein said alkyl group preferably includes at least one        tertiary or quaternary carbon atom, wherein said vinyl ester        monomer is present in an amount of from about 5 mol % to about        45 mol %, more preferably from about 10 mol % to about 30 mol %,        and even more preferably from about 10 mol % to about 20 mol %;        and    -   B) vinyl ether monomer(s), represented by formula CH₂═CR³—OR⁴        respectively, wherein R³ is independently either hydrogen or a        methyl group, preferably hydrogen, and wherein R⁴ is selected        from the group consisting of a substituted or unsubstituted        straight-chain or branched-chain, preferably straight chain,        alkyl group having 1 to 3 carbon atoms, preferably 2 carbon        atoms, said vinyl ether monomer(s) preferably being present in        amounts of from about 10 mol % to about 40 mol %, more        preferably from about 5 mol % to about 45 mol %, more preferably        from about 10 mol % to about 30 mol %, and even more preferably        from about 10 mol % to about 20 mol %; and

(4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether representedby formula CH₂═CR³—O—R⁵—OH, where R³ is methyl or hydrogen, preferablyhydrogen, and R⁵ is selected from the group consisting a substituted orunsubstituted straight-chain or branched-chain C3 to C5 alkyl,preferably C4, unsubstituted straight-chain alkyl group, wherein theamount of said third monomer is preferably present in an amount of fromabout 3 mol % to about 30 mol %.

CoPolymer Formation Methods

It will be appreciated by those skilled in the art, based on theteachings contained herein, that copolymers of the present invention maybe formed to achieve the preferred characteristics described hereinusing a variety of techniques, and all such techniques are within thescope of the present invention.

In preferred embodiments, the fluorocopolymer is preferably produced ina polymerization system that utilizes a carrier for the monomer/polymerduring and/or after formation. According to one preferred embodiment thecarrier acts as a solvent and/or dispersant for the monomer and/orpolymer, and such operations include dispersion, emulsion and solutionpolymerization. Examples of carriers in such systems, includingpreferably solvents for solution polymerization, include: esters, suchas methyl acetate, ethyl acetate, propyl acetate and butyl acetate;ketones, such as acetone, methyl ethyl acetone and cyclohexanone;aliphatic hydrocarbons, such as hexane, cyclohexane, octane, nonane,decane, undecane, dodecane and mineral spirits; aromatic hydrocarbons,such as benzene, toluene, xylene, naphthalene, and solvent napthta;alcohols, such as methanol, ethanol, tert-butanol, iso-propanol,ethylene glycol monoalkyl ethers; cyclic ethers, such astetrahydrofuran, tetrahydropyran, and dioxane; fluorinated solvents,such as HCFC-225 and HCFC-141b; dimethyl sulfoxide; and the mixturesthereof.

It is contemplated that the temperature conditions used in thepolymerization process of the present invention can be varied accordingto the particular equipment and applications involved and all suchtemperatures are within the scope of the present invention. Preferably,the polymerization is conducted at a temperature in a range of fromabout 30° C. to about 150° C., more preferably from about 40° C. toabout 100° C., and even more preferably from about 50° C. to about 70°C., depending on factors such as the polymerization initiation sourceand type of the polymerization medium.

In certain preferred embodiments, it is preferred that the solutionpolymerization is conducted under conditions under which the totalamount of the solvent used in the copolymerization process, based on theweight of the solvent and monomer in the solution, is from about 10 wt %to about 40 wt %, more preferably in amounts of from about 10 wt % toabout 30 wt %, and more preferably in certain embodiments in an amountof from about 15% to about 25%. In certain of such embodiments, thesolvent used in the solution copolymerization process comprises,preferably consists essentially of, and more preferably in certainembodiments consists of C2-C5 alkyl acetate, and even more preferablybutyl acetate.

In preferred embodiments, the copolymer as formed in accordance with thepreferred methods described herein is prepared by copolymerizing thosemonomers under conditions effective to achieve a copolymer having anumber average molecular weight of 5000 to 50,000, or is someembodiments 5000 to 10,000 as measured by gel phase chromatography(“GPC”) according to the method described in Skoog, D. A. Principles ofInstrumental Analysis, 6th ed.; Thompson Brooks/Cole: Belmont, Calif.,2006, Chapter 28, which is incorporated herein by reference. In certainembodiments, the copolymer has a number average molecular weight that isgreater than about 10,000, and even more preferably from 10,000 to about14,000. According to certain preferred embodiments, the copolymer has amolecular weight distribution of 2 to 10, more preferably 2.5 to 8, andmost preferably 3 to 6. Applicants have found that in certainembodiments the use of copolymers having a molecular weight less than5000 produces weatherability and chemical resistance of the protectivecoating that is less than is desired for some applications and that whenthe polymers have a molecular weight of more than 50,000, coatingcompositions having viscosities that may negatively impact the spreadingor coating properties of the coating compositions and hence difficultiesin the coating operations.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of HFO-1234ze, with            said HFO-1234ze preferably comprising, consisting            essentially of or consisting of trans-HFO-1234ze, preferably            in an amount of from about 20 mol % to about 30 mol %, and            even more preferably from about 22 mol % to about 27.5 mol            %, and even more preferably about 25 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %, (3)            third monomers comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is                either hydrogen or a methyl group, preferably hydrogen,                and wherein R² is an unsubstituted branched-chain alkyl                group having 6 to 8 carbon atoms, wherein said alkyl                group preferably includes at least one tertiary or                quaternary carbon atom, wherein said vinyl ester monomer                is present in an amount of from about 5 mol % to about                45 mol %, more preferably from about 10 mol % to about                30 mol %, and even more preferably from about 10 mol %                to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is either hydrogen or a methyl                group, preferably hydrogen, and wherein R⁴ is selected                from the group consisting of a substituted or                unsubstituted straight-chain or branched-chain,                preferably straight chain, alkyl group having 1 to 3                carbon atoms, preferably 2 carbon atoms, said vinyl                ether monomer(s) preferably being present in amounts of                from about 10 mol % to about 40 mol %, more preferably                from about 5 mol % to about 45 mol %, more preferably                from about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            methyl or hydrogen, preferably hydrogen, and R⁵ is selected            from the group consisting of a C3 to C5, preferably C4,            unsubstituted straight-chain alkyl group, wherein the amount            of said third monomer is preferably from about 3 mol % to            about 30 mol %; and    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising one or more VOC compounds and preferably        selected from aromatic hydrocarbons such as xylene and toluene;        alcohols such as n-butanol; esters such as butyl acetate;        ketones such as methyl isobutyl ketone, and glycol ethers such        as ethyl cellusolve, with C2-C5 alkyl acetate being preferred,        and even more preferably comprising, consisting essentially of,        or consisting of butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier to produce a polymeric composition comprising not        greater than about 30% by weight of said carrier, preferably        with a solids content of at least about 70% by weight. According        to preferred embodiments, the fluorocopolymer composition of the        present invention, and in particular the fluorocopolymer formed        as described in the preceding sentence, has a polymer number        average molecular weight as measured by gel phase chromatography        (“GPC”) according to the method described in Skoog, D. A.        Principles of Instrumental Analysis, 6th ed.; Thompson        Brooks/Cole: Belmont, Calif., 2006, Chapter 28, which is        incorporated herein by reference, of from about 5000 and 50,000,        more preferably from about 7000 to about 15000 and has a solids        content of from about 70% to about 90% by weight, and even more        preferably from about 70% to about 85% by weight, and preferably        a VOC content of less than about 400 g/l, more preferably from        about 400 g/l to about 100 g/l, and even more preferably from        about 350 g/l to about 200 g/l. It is also preferred in such        embodiments as described in the present application in general,        and in this paragraph as in particular, that the coating        compositions of the present invention have a viscosity at 25° C.        of less than about 1900 mPa-s, more preferably less than about        1800 mPa-s and even more preferably of less than about 1700        mPa-s as measured by Ford Cup at least at one of 12 revolutions        per minutes (r/m), 30 r/m and 60 r/m, and preferably at all        three speeds, preferably as measured according to ASTM        D1200-10(2014) or ASTM D2196 as appropriate.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of HFO-1234ze, with            said HFO-1234ze preferably comprising, consisting            essentially of or consisting of trans-HFO-1234ze in an            amount of from about 40 mol % to about 60 mol %, and even            more preferably from about 45 mol % to about 55 mol %, and            even more preferably about 50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is                either hydrogen or a methyl group, preferably hydrogen,                and wherein R² is an unsubstituted branched-chain alkyl                group having 6 to 8 carbon atoms including at least one                tertiary carbon atom, wherein said vinyl ester monomer                is present in an amount of from about 5 mol % to about                45 mol %, more preferably from about 10 mol % to about                30 mol %, and even more preferably from about 10 mol %                to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is either hydrogen or a methyl                group, preferably hydrogen, and wherein R⁴ is selected                from the group consisting of a substituted or                unsubstituted straight-chain or branched-chain,                preferably straight chain, alkyl group having 1 to 3                carbon atoms, preferably 2 carbon atoms, said vinyl                ether monomer(s) preferably being present in amounts of                from about 10 mol % to about 40 mol %, more preferably                from about 5 mol % to about 45 mol %, more preferably                from about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            either hydrogen or a methyl group and R⁵ is selected from            the group consisting of a substituted or unsubstituted            straight-chain or branched-chain C3 to C5 alkyl, preferably            C4, unsubstituted straight-chain alkyl group, wherein the            amount of said third monomer is preferably from about 3 mol            % to about 30 mol %; and    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising one or more VOC compounds selected from        aromatic hydrocarbons such as xylene and toluene; alcohols such        as n-butanol; esters such as butyl acetate; ketones such as        methyl isobutyl ketone, and glycol ethers such as ethyl        cellusolve, with C2-C5 alkyl acetate being preferred, and even        more preferably comprising, consisting essentially of, or        consisting of butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier to produce a polymeric composition comprising not        greater than about 30% by weight of said carrier, preferably        with a solids content of at least about 70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of HFO-1234ze, with            said HFO-1234ze preferably comprising, consisting            essentially of or consisting of trans-HFO-1234ze, preferably            in an amount of from about 40 mol % to about 60 mol %, and            even more preferably from about 45 mol % to about 55 mol %,            and even more preferably about 50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is a                methyl group, preferably hydrogen, and wherein R² is an                unsubstituted branched-chain alkyl group having 6 to 8                carbon atoms, wherein said alkyl group preferably                includes at least one tertiary carbon atom, wherein said                vinyl ester monomer is present in an amount of from                about 5 mol % to about 45 mol %, more preferably from                about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is a is either hydrogen or a                methyl group, and wherein R⁴ is selected from the group                consisting of a substituted or unsubstituted                straight-chain or branched-chain, preferably straight                chain, alkyl group having 1 to 3 carbon atoms,                preferably 2 carbon atoms, said vinyl ether monomer(s)                preferably being present in amounts of from about 10 mol                % to about 40 mol %, more preferably from about 5 mol %                to about 45 mol %, more preferably from about 10 mol %                to about 30 mol %, and even more preferably from about                10 mol % to about 20 mol %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            methyl or hydrogen, preferably hydrogen, and R⁵ is selected            from the group consisting of an a substituted or            unsubstituted straight-chain or branched-chain C3 to C5            alkyl, preferably C4, unsubstituted straight-chain alkyl            group, wherein the amount of said third monomer is            preferably from about 3 mol % to about 30 mol %; and    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising one or more VOC compounds and preferably        selected from aromatic hydrocarbons such as xylene and toluene;        alcohols such as n-butanol; esters such as butyl acetate;        ketones such as methyl isobutyl ketone, and glycol ethers such        as ethyl cellusolve, with C2-C5 alkyl acetate being preferred,        and even more preferably comprising, consisting essentially of,        or consisting of butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier to produce a polymeric composition comprising not        greater than about 30% by weight of said carrier, preferably        with a solids content of at least about 70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of trans-HFO-1234ze            in an amount of from about 40 mol % to about 60 mol %, and            even more preferably from about 45 mol % to about 55 mol %,            and even more preferably about 50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is                either hydrogen or a methyl group, preferably hydrogen,                and wherein R² is an unsubstituted branched-chain alkyl                group having 6 to 8 carbon atoms including at least one                quaternary carbon atom, wherein said vinyl ester monomer                is present in an amount of from about 5 mol % to about                45 mol %, more preferably from about 10 mol % to about                30 mol %, and even more preferably from about 10 mol %                to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is either hydrogen or a methyl                group, preferably hydrogen, and wherein R⁴ is selected                from the group consisting of a substituted or                unsubstituted straight-chain or branched-chain,                preferably straight chain, alkyl group having 1 to 3                carbon atoms, preferably 2 carbon atoms, said vinyl                ether monomer(s) preferably being present in amounts of                from about 10 mol % to about 40 mol %, more preferably                from about 5 mol % to about 45 mol %, more preferably                from about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            either hydrogen or a methyl group and R⁵ is selected from            the group consisting of a substituted or unsubstituted            straight-chain or branched-chain C3 to C5 alkyl, preferably            C4, unsubstituted straight-chain alkyl group, wherein the            amount of said third monomer is preferably from about 3 mol            % to about 30 mol %; and    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising one or more VOC compounds selected from        aromatic hydrocarbons such as xylene and toluene; alcohols such        as n-butanol; esters such as butyl acetate; ketones such as        methyl isobutyl ketone, and glycol ethers such as ethyl        cellusolve, with C2-C5 alkyl acetate being preferred, and even        more preferably comprising, consisting essentially of, or        consisting of butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier and said light stabilizer to produce a polymeric        composition comprising not greater than about 30% by weight of        said carrier, preferably with a solids content of at least about        70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of HFO-1234ze, with            said HFO-1234ze preferably comprising, consisting            essentially of or consisting of trans-HFO-1234ze, preferably            in an amount of from about 40 mol % to about 60 mol %, and            even more preferably from about 45 mol % to about 55 mol %,            and even more preferably about 50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is a                methyl group, and wherein R² is an unsubstituted                branched-chain alkyl group having 6 to 8 carbon atoms,                wherein said alkyl group preferably includes at least                one quaternary carbon atom, wherein said vinyl ester                monomer is present in an amount of from about 5 mol % to                about 45 mol %, more preferably from about 10 mol % to                about 30 mol %, and even more preferably from about 10                mol % to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is a methyl group, and wherein                R⁴ is selected from the group consisting of a                substituted or unsubstituted straight-chain or                branched-chain, preferably straight chain, alkyl group                having 1 to 3 carbon atoms, preferably 2 carbon atoms,                said vinyl ether monomer(s) preferably being present in                amounts of from about 10 mol % to about 40 mol %, more                preferably from about 5 mol % to about 45 mol %, more                preferably from about 10 mol % to about 30 mol %, and                even more preferably from about 10 mol % to about 20 mol                %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            methyl or hydrogen, preferably hydrogen, and R⁵ is selected            from the group consisting of a substituted or unsubstituted            straight-chain or branched-chain C3 to C5 alkyl, preferably            C4, unsubstituted straight-chain alkyl group, wherein the            amount of said third monomer is preferably from about 3 mol            % to about 30 mol %; and    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising one or more VOC compounds and preferably        selected from aromatic hydrocarbons such as xylene and toluene;        alcohols such as n-butanol; esters such as butyl acetate;        ketones such as methyl isobutyl ketone, and glycol ethers such        as ethyl cellusolve, with C2-C5 alkyl acetate being preferred,        and even more preferably comprising, consisting essentially of,        or consisting of butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier and said light stabilizer to produce a polymeric        composition comprising not greater than about 30% by weight of        said carrier, preferably with a solids content of at least about        70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of trans-HFO-1234ze            in an amount of from about 40 mol % to about 60 mol %, and            even more preferably from about 45 mol % to about 55 mol %,            and even more preferably about 50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is                either hydrogen or a methyl group, preferably hydrogen,                and wherein R² is an unsubstituted branched-chain alkyl                group having 6 to 8 carbon atoms including at least one                tertiary carbon atom, wherein said vinyl ester monomer                is present in an amount of from about 5 mol % to about                45 mol %, more preferably from about 10 mol % to about                30 mol %, and even more preferably from about 10 mol %                to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is a methyl group and wherein                R⁴ is selected from consisting of a substituted or                unsubstituted straight-chain or branched-chain,                preferably straight chain, alkyl group having 1 to 3                carbon atoms, preferably 2 carbon atoms, said vinyl                ether monomer(s) preferably being present in amounts of                from about 10 mol % to about 40 mol %, more preferably                from about 5 mol % to about 45 mol %, more preferably                from about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            either hydrogen or a methyl group, preferably hydrogen, and            R⁵ is selected from the group consisting of a substituted or            unsubstituted straight-chain or branched-chain C3 to C5            alkyl, preferably C4, unsubstituted straight-chain alkyl            group, wherein the amount of said third monomer is            preferably from about 3 mol % to about 30 mol %; and    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising one or more VOC compounds selected from        aromatic hydrocarbons such as xylene and toluene; alcohols such        as n-butanol; esters such as butyl acetate; ketones such as        methyl isobutyl ketone, and glycol ethers such as ethyl        cellusolve, with C2-C5 alkyl acetate being preferred, and even        more preferably comprising, consisting essentially of, or        consisting of butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier and said light stabilizer to produce a polymeric        composition comprising not greater than about 30% by weight of        said carrier, preferably with a solids content of at least about        70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of HFO-1234ze, with            said HFO-1234ze preferably comprising, consisting            essentially of or consisting of trans-HFO-1234ze, preferably            in an amount of from about 40 mol % to about 60 mol %, and            even more preferably from about 45 mol % to about 55 mol %,            and even more preferably about 50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is a                methyl group, and wherein R² is an unsubstituted                branched-chain alkyl group having 6 to 8 carbon atoms,                wherein said alkyl group preferably includes at least                one quaternary carbon atom, wherein said vinyl ester                monomer is present in an amount of from about 5 mol % to                about 45 mol %, more preferably from about 10 mol % to                about 30 mol %, and even more preferably from about 10                mol % to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is a methyl group and wherein                R⁴ is selected from the group consisting of a                substituted or unsubstituted straight-chain or                branched-chain, preferably straight chain, alkyl group                having 1 to 3 carbon atoms, preferably 2 carbon atoms,                said vinyl ether monomer(s) preferably being present in                amounts of from about 10 mol % to about 40 mol %, more                preferably from about 5 mol % to about 45 mol %, more                preferably from about 10 mol % to about 30 mol %, and                even more preferably from about 10 mol % to about 20 mol                %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            methyl or hydrogen, preferably hydrogen, and R⁵ is selected            from the group consisting of a substituted or unsubstituted            straight-chain or branched-chain C3 to C5 alkyl, preferably            C4, unsubstituted straight-chain alkyl group, wherein the            amount of said third monomer is preferably from about 3 mol            % to about 30 mol %; and    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising one or more VOC compounds and preferably        selected from aromatic hydrocarbons such as xylene and toluene;        alcohols such as n-butanol; esters such as butyl acetate;        ketones such as methyl isobutyl ketone, and glycol ethers such        as ethyl cellusolve, with C2-C5 alkyl acetate being preferred,        and even more preferably comprising, consisting essentially of,        or consisting of butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier and said light stabilizer to produce a polymeric        composition comprising not greater than about 30% by weight of        said carrier, preferably with a solids content of at least about        70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of trans-HFO-1234ze            in an amount of from about 40 mol % to about 60 mol %, and            even more preferably from about 45 mol % to about 55 mol %,            and even more preferably about 50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is                hydrogen, and wherein R² is an unsubstituted                branched-chain alkyl group having 6 to 8 carbon atoms                including at least one quaternary carbon atom, wherein                said vinyl ester monomer is present in an amount of from                about 5 mol % to about 45 mol %, more preferably from                about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is either hydrogen or a methyl                group, preferably hydrogen, and wherein R⁴ is selected                from the group consisting of a substituted or                unsubstituted branched-chain alkyl group having 1 to 3                carbon atoms, preferably 2 carbon atoms, said vinyl                ether monomer(s) preferably being present in amounts of                from about 10 mol % to about 40 mol %, more preferably                from about 5 mol % to about 45 mol %, more preferably                from about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            either hydrogen or a methyl group and R⁵ is selected from            the group consisting of a C3 to C5, preferably C4,            unsubstituted straight-chain alkyl group, wherein the amount            of said third monomer is preferably from about 3 mol % to            about 30 mol %; and    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising one or more VOC compounds selected from        aromatic hydrocarbons such as xylene and toluene; alcohols such        as n-butanol; esters such as butyl acetate; ketones such as        methyl isobutyl ketone, and glycol ethers such as ethyl        cellusolve, with C2-C5 alkyl acetate being preferred, and even        more preferably comprising, consisting essentially of, or        consisting of butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier and said light stabilizer to produce a polymeric        composition comprising not greater than about 30% by weight of        said carrier, preferably with a solids content of at least about        70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of HFO-1234ze, with            said HFO-1234ze preferably comprising, consisting            essentially of or consisting of trans-HFO-1234ze, preferably            in an amount of from about 40 mol % to about 60 mol %, and            even more preferably from about 45 mol % to about 55 mol %,            and even more preferably about 50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is a                methyl group, and wherein R² is an unsubstituted                branched-chain alkyl group having 6 to 8 carbon atoms,                wherein said alkyl group preferably includes at least                one quaternary carbon atom, wherein said vinyl ester                monomer is present in an amount of from about 5 mol % to                about 45 mol %, more preferably from about 10 mol % to                about 30 mol %, and even more preferably from about 10                mol % to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is a methyl group, and wherein                R⁴ is selected from the group consisting of a                substituted or unsubstituted straight-chain or                branched-chain, preferably straight chain, alkyl group                having 1 to 3 carbon atoms, preferably 2 carbon atoms,                said vinyl ether monomer(s) preferably being present in                amounts of from about 10 mol % to about 40 mol %, more                preferably from about 5 mol % to about 45 mol %, more                preferably from about 10 mol % to about 30 mol %, and                even more preferably from about 10 mol % to about 20 mol                %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            methyl, and R⁵ is selected from the group consisting of a C3            to C5, preferably C4, unsubstituted straight-chain alkyl            group, wherein the amount of said third monomer is            preferably from about 3 mol % to about 30 mol %;    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising one or more VOC compounds and preferably        selected from aromatic hydrocarbons such as xylene and toluene;        alcohols such as n-butanol; esters such as butyl acetate;        ketones such as methyl isobutyl ketone, and glycol ethers such        as ethyl cellusolve, with C2-C5 alkyl acetate being preferred,        and even more preferably comprising, consisting essentially of,        or consisting of butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier and said light stabilizer to produce a polymeric        composition comprising not greater than about 30% by weight of        said carrier, preferably with a solids content of at least about        70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of HFO-1234ze, with            said HFO-1234ze preferably comprising, consisting            essentially of or consisting of trans-HFO-1234ze, preferably            in an amount of from about 40 mol % to about 60 mol %, and            even more preferably from about 45 mol % to about 55 mol %,            and even more preferably about 50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is                hydrogen or a methyl group, preferably hydrogen, and                wherein R² is an unsubstituted branched-chain alkyl                group having 6 to 8 carbon atoms, wherein said alkyl                group preferably includes at least one quaternary carbon                atom, wherein said vinyl ester monomer is present in an                amount of from about 5 mol % to about 45 mol %, more                preferably from about 10 mol % to about 30 mol %, and                even more preferably from about 10 mol % to about 20 mol                %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is hydrogen or a methyl group,                preferably hydrogen, and wherein R⁴ is selected from the                group consisting of a substituted or unsubstituted                straight-chain or branched-chain, preferably straight                chain, alkyl group having 1 to 3 carbon atoms,                preferably 2 carbon atoms, said vinyl ether monomer(s)                preferably being present in amounts of from about 10 mol                % to about 40 mol %, more preferably from about 5 mol %                to about 45 mol %, more preferably from about 10 mol %                to about 30 mol %, and even more preferably from about                10 mol % to about 20 mol %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            hydrogen or methyl, preferably hydrogen, and R⁵ is selected            from the group consisting of a C3 to C5, preferably C4,            unsubstituted straight-chain alkyl group, wherein the amount            of said third monomer is preferably from about 3 mol % to            about 30 mol %; and    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising one or more VOC compounds selected from        aromatic hydrocarbons such as xylene and toluene; alcohols such        as n-butanol; esters such as butyl acetate; ketones such as        methyl isobutyl ketone, and glycol ethers such as ethyl        cellusolve, with C2-C5 alkyl acetate being preferred, and even        more preferably comprising, consisting essentially of, or        consisting of butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier and said light stabilizer to produce a polymeric        composition comprising not greater than about 30% by weight of        said carrier, preferably with a solids content of at least about        70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of            trans-HFO-1234ze, preferably in an amount of from about 40            mol % to about 60 mol %, and even more preferably from about            45 mol % to about 55 mol %, and even more preferably about            50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is                hydrogen or methyl, preferably hydrogen, and wherein R²                is an unsubstituted branched-chain alkyl group having 6                to 8 carbon atoms, wherein said alkyl group preferably                includes at least one quaternary carbon atom, wherein                said vinyl ester monomer is present in an amount of from                about 5 mol % to about 45 mol %, more preferably from                about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is hydrogen or methyl,                preferably hydrogen, and wherein R⁴ is straight chain                alkyl group having 2 carbon atoms, said vinyl ether                monomer(s) preferably being present in amounts of from                about 10 mol % to about 40 mol %, more preferably from                about 5 mol % to about 45 mol %, more preferably from                about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            hydrogen or methyl, preferably hydrogen, and R⁵ is selected            from the group consisting of a C3 to C5, preferably C4,            unsubstituted straight-chain alkyl group, wherein the amount            of said third monomer is preferably from about 3 mol % to            about 30 mol %; and    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising at least about 50% by weight of C2-C5        alkyl acetate and even more preferably butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier and said light stabilizer to produce a polymeric        composition comprising not greater than about 30% by weight of        said carrier, preferably with a solids content of at least about        70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of            trans-HFO-1234ze, preferably in an amount of from about 40            mol % to about 60 mol %, and even more preferably from about            45 mol % to about 55 mol %, and even more preferably about            50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is                hydrogen or methyl, preferably hydrogen, and wherein R²                is an unsubstituted branched-chain alkyl group having 6                to 8 carbon atoms, wherein said alkyl group preferably                includes at least one quaternary carbon atom, wherein                said vinyl ester monomer is present in an amount of from                about 5 mol % to about 45 mol %, more preferably from                about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is hydrogen or methyl,                preferably hydrogen, and wherein R⁴ is straight chain                alkyl group having 2 carbon atoms, said vinyl ether                monomer(s) preferably being present in amounts of from                about 10 mol % to about 40 mol %, more preferably from                about 5 mol % to about 45 mol %, more preferably from                about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            hydrogen or methyl, preferably hydrogen, and R⁵ is selected            from the group consisting of a C3 to C5, preferably C4,            unsubstituted straight-chain alkyl group, wherein the amount            of said third monomer is preferably from about 3 mol % to            about 30 mol %;    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising at least about 50% by weight of C2-C5        alkyl acetate and even more preferably butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier and said light stabilizer to produce a polymeric        composition comprising not greater than about 30% by weight of        said carrier, preferably with a solids content of at least about        70% by weight.

In preferred embodiments, the formation of fluorocopolymer coatingcompositions comprises, and preferably consists essentially of:

-   -   (i) providing one or more fluorocopolymers by copolymerization        of        -   (1) first monomer consisting essentially of            trans-HFO-1234ze, preferably in an amount of from about 40            mol % to about 60 mol %, and even more preferably from about            45 mol % to about 55 mol %, and even more preferably about            50 mol %,        -   (2) second monomer(s) consisting essentially of CTFE,            preferably in an amount of from about 20 mol % to about 30            mol %, and even more preferably from about 22 mol % to about            27.5 mol %, and even more preferably about 25 mol %,        -   (3) third monomer(s) comprising:            -   A) vinyl ester monomer represented by formula                CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and wherein R¹ is                hydrogen, and wherein R² is an unsubstituted                branched-chain alkyl group having 6 to 8 carbon atoms,                wherein said alkyl group preferably includes at least                one quaternary carbon atom, wherein said vinyl ester                monomer is present in an amount of from about 5 mol % to                about 45 mol %, more preferably from about 10 mol % to                about 30 mol %, and even more preferably from about 10                mol % to about 20 mol %; and            -   B) vinyl ether monomer(s), represented by formula                CH₂═CR³—O—R⁴, wherein R³ is hydrogen and R⁴ is selected                from the group consisting of a substituted or                unsubstituted branched-chain alkyl group having 1 to 3                carbon atoms, preferably 2 carbon atoms, said vinyl                ether monomer(s) preferably being present in amounts of                from about 10 mol % to about 40 mol %, more preferably                from about 5 mol % to about 45 mol %, more preferably                from about 10 mol % to about 30 mol %, and even more                preferably from about 10 mol % to about 20 mol %; and        -   (4) fourth monomer(s) consisting of hydroxyalkyl vinyl ether            represented by the formula CH₂═CR³—O—R⁵—OH, where R³ is            hydrogen, and R⁵ is a C4 unsubstituted straight-chain alkyl            group, wherein the amount of said third monomer is            preferably from about 3 mol % to about 30 mol %;    -   (ii) providing a carrier for said one or more fluorocopolymers,        said carrier comprising at least about 50% by weight of C2-C5        alkyl acetate and even more preferably butyl acetate; and    -   (iii) combining said one or more fluorocopolymers with said        carrier and said light stabilizer to produce a polymeric        composition comprising not greater than about 30% by weight of        said carrier, preferably with a solids content of at least about        70% by weight.

According to preferred embodiments, the fluorocopolymer composition ofthe present invention has a polymer number average molecular weight asmeasured by gel phase chromatography (“GPC”) according to the methoddescribed in Skoog, D. A. Principles of Instrumental Analysis, 6th ed.;Thompson Brooks/Cole: Belmont, Calif., 2006, Chapter 28, which isincorporated herein by reference, of from about 5000 and 50,000, morepreferably from about 7000 to about 15,000 and has a solids content offrom about 70% to about 90% by weight, and even more preferably fromabout 70% to about 85% by weight, and preferably a VOC content of lessthan about 400 g/l, more preferably from about 400 g/l to about 100 g/l,and even more preferably from about 350 g/l to about 200 g/l. It is alsopreferred in such embodiments as described in the present application ingeneral, and in this paragraph in particular, that the coatingcompositions of the present invention have a viscosity at 25° C. of lessthan about 1900 mPa-s, more preferably less than about 1800 mPa-s andeven more preferably of less than about 1700 mPa-s as measured by FordCup at least at one of 12 revolutions per minutes (r/m), 30 r/m and 60r/m, and preferably at all three speeds, preferably as measuredaccording to ASTM D1200-10(2014) or ASTM D2196 as appropriate.

Coating Composition Formation Methods

The copolymers as formed in accordance with the procedures describedherein may then be used to form various coating compositions that havethe substantial advantages described above. For example, varioussolvents can be used for the preparation of solution-type paints orcoatings by adding those solvents to the fluorocopolymer of the presentinvention formed as described herein. In certain embodiments, preferredsolvents for formation of the coating composition include aromatichydrocarbons such as xylene and toluene; alcohols such as n-butanol;esters such as butyl acetate; ketones such as methyl isobutyl ketone,and glycol ethers such as ethyl cellusolve and various commercialthinners.

In certain embodiments, the coating composition of the present inventionhas a solid content of from about 70% to about 90% by weight based onthe total weight of the coating composition, and more preferably incertain embodiments from about 75% go about 85% by weight of solids. Incertain preferred embodiments, the solids comprise and preferablyconsist essentially of the copolymers of the present invention and/orcross-linked copolymers formed using the copolymers of the presentinvention. Although it is contemplated that those skilled in the artwill be able to form coatings using the present compositions accordingto anyone of known methods, in preferred embodiment the coating isformed by brushing, a rolling, air spraying, airless spraying, flowcoating, roller coating, a spin coating, and the like and anycombination of these may be used. Furthermore, the coating can beapplied on various substrates. The coating film can be formed directlyon a substrate or via a primer or if necessary, via an undercoatinglayer. Although all thicknesses are within the scope of the presentinvention, in preferred embodiments the outermost cured coating filmlayer has a layer thickness of from about 20 to about 30 m.

EXAMPLES

The present invention is further illustrated by the followingnon-limiting examples.

Example 1—Fluoropolymer Preparation

A solution polymerization operation is carried out by charging into a300 ml stainless steel autoclave equipped with a stirrer the componentsas indicated in the following Table 1A:

TABLE 1A Mono- Mono- COMPONENT Weight, mer mer, TYPE NAME grams Wt %Moles mol % Solvent toluene 120 56.56 First Monomer trans-1,3,3,3- 9.2427.2 0.17 25.32 (fluoropolymer) tetrafluoropropene (trans-HFO- 1234ze)Second CTFE 9.38 0.17 25.32 Monomer Third Monomer VEOVA-10 23.63 11.140.12 17.58 (vinyl ester) Third Monomer ethyl vinyl ether 8.6 4.05 0.1218.09 (ethyl vinyl ether) Fourth hydroxybutylvinyl 10.83 5.1 0.19 13.75Monomer ether (alkylhydroxy ether) Initiator tertbutylper- 0.2 0.16oxypivalate

The toluene, the ethyl vinyl ether monomer, the vinyl ester monomer(VEOVA-10), the hydroxybutyl vinyl ether, the initiator and 0.8 grams ofzinc oxide were charged into the vessel. The mixture was solidified withliquid nitrogen, and deaerated to remove the dissolved air. Then thetrans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze) and CTFE was addedto the mixture in the autoclave, and the mixture was then graduallyheated to about 75° C. The mixture was then stirred for about 4 hours tocarry-out solution copolymerization of the monomers. After the autoclavewas cooled to room temperature, any unreacted monomers were purged andthen the autoclave was opened and a vacuum was applied to the autoclavefor a sufficient period of time to remove sufficient excess solvent toachieve a solid content (copolymer content) in the autoclave of about50-80% by weight. The final fluorocopolymer (without solvent) was testedand found to have: a number average molecular weight (Mn) of about13,600 and a Mw/Mn of 2.3; a hydroxyl value of 96 mg KOH/g; a Fluorinecontent of 17.5% and a Chlorine content of 14.4%. The resultingcopolymer plus solvent combination was in the form of a clear solutionhaving a solid, that is, copolymer, content of about 70% and a VOCcontent of about 400 g/l.

The solvent/polymer resulting from the operation described about is thenadded to each of the materials identified in Table 1B below on a 1:1weight basis and is found to form a clear solution at room temperature:

TABLE 1B Solubility Test (1:1 wt ratio) Solvent Appearance MethanolClear solution Ethanol Clear solution Petroleum Ether Clear solutionn-Hexane Clear solution Xylene Clear solution Toluene Clear solutionMethyl Ethyl Ketone Clear solution Acetone Clear solution PropyleneGlycol Clear solution Monomethyl Ether Acetate (PMA) Butyl Acetate Clearsolution THE Clear solution

The result reported above indicates that the fluorocopolymer accordingto the present invention is capable of forming solutions with manymaterials that may be used in or form a substantial part of formulationsfor protective coatings, and accordingly the present fluorocopolymer hasexcellent usefulness in the formation of protective coatings inconjunction with a wide variety of materials that may be used, forexample, as supplemental carriers in such coating compositions.

Example 2—Coating Composition and Coating Properties

A coating composition in the form of a white paste is formed by addingbutyl acetate as thinner into copolymer solution formed in Example 1 toobtain a solution with a solid content of about 30-40 wt %. Thissolution is then charged into a glass flask and agitated at 250 rpm. Avacuum is then pulled on the flask until the vacuum reached about 100 Pawhile maintaining the temperature of the copolymer solution at 18±1° C.The distilled solution is collected in a cold trap and monitored byGC-MS until no unreacted monomers, including HFO-1234ze and ethyl vinylether, or solvent were detected. The vacuum pump, agitation andtemperature control is discontinued. Then ZnO was removed off byfiltration. A transparent and colorless copolymer solution was obtained.After that, added Al₂O₃ molecular sieve A202-HF, a UOP product (8.0 wt %of the total polymer weight) or molecular sieve P188, a UOP product (2.0wt % of the total polymer weight) or Al₂O₃ powder (7% wt) were addedinto the clear copolymer solution and the solution is heated to 87±2° C.for 14-18 hours with 250 rpm agitation. Agitation is then stopped, theglass flask is cooled to room temperature, the Al₂O₃ molecular sieve wasremoved off by filtration, a clear solution was obtained. The solutionwas then condensed to 50-80 wt % solid content.

Example 3—Fluoropolymer Preparation

A solution polymerization operation is carried out by charging into a300 ml stainless steel autoclave equipped with a stirrer the componentsas indicated in the following Table 3A:

TABLE 3A Mono- Mono- COMPONENT Weight, mer mer, TYPE NAME grams Wt %Moles mol % Solvent butyl acetate 120 56.56 First Monomer trans-1,3,3,3-19.6 27.2 0.17 25.32 (fluoropolymer) tetrafluoropropene (trans-HFO-1234ze) Second CTFE 19.9 0.17 25.32 Monomer Third Monomer VEOVA-10 23.6311.14 0.12 17.58 (vinyl ester) Third Monomer ethyl vinyl ether 8.6 4.050.12 18.09 (ethyl vinyl ether) Fourth hydroxybutylvinyl 10.83 5.1 0.1913.75 Monomer ether (alkylhydroxy ether) Initiator tertbutylper- 0.20.16 oxypivalate

The toluene, the ethyl vinyl ether monomer, the vinyl ester monomer(VEOVA-10), the hydroxybutyl vinyl ether, the initiator and 2 grams ofzinc oxide were charged into the vessel. The mixture was solidified withliquid nitrogen, and deaerated to remove the dissolved air. Then thetrans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze) and CTFE was addedto the mixture in the autoclave, and the mixture was then graduallyheated to about 75° C. The mixture was then stirred for about 4 hours tocarry-out solution copolymerization of the monomers. After the autoclavewas cooled to room temperature, any unreacted monomers were purged andthen the autoclave was opened and a vacuum was applied to the autoclavefor a sufficient period of time to remove sufficient excess solvent toachieve a solid content (copolymer content) in the autoclave of about50-80% by weight. The final fluorocopolymer (without solvent) was testedand found to have: a number average molecular weight (Mn) of about 18000and a Mw/Mn of 3.2; a hydroxyl value of 72 mg KOH/g; a Fluorine contentof 16% and a Chlorine content of 15%. The resulting copolymer plussolvent combination was in the form of a clear solution having a solid,that is, copolymer, content of about 70% and a VOC content of about 400g/l.

The solvent/polymer resulting from the operation described above is thenadded to each of the materials identified in Table 3B below on a 1:1weight basis and is found to form a clear solution at room temperature:

TABLE 3B Solubility Test (1:1 wt ratio) Solvent Appearance MethanolClear solution Ethanol Clear solution Petroleum Ether Clear solutionn-Hexane Clear solution Xylene Clear solution Toluene Clear solutionMethyl Ethyl Ketone Clear solution Acetone Clear solution PropyleneGlycol Clear solution Monomethyl Ether Acetate(PMA) Butyl Acetate Clearsolution THE Clear solution

The result reported above indicates that the fluorocopolymer accordingto the present invention is capable of forming solutions with manymaterials that may be used in or form a substantial part of formulationsfor protective coatings, and accordingly the present fluorocopolymer hasexcellent usefulness in the formation of protective coatings inconjunction with a wide variety of materials that may be used, forexample, as supplemental carriers in such coating compositions.

Example 4—Coating Composition and Coating Properties

A coating composition in the form of a white paste is formed by addingbutyl acetate as thinner into copolymer solution formed in Example 3 toobtain a solution with a solid content of about 30-40 wt %. Thissolution is then charged into a glass flask and agitated at 250 rpm. Avacuum is then pulled on the flask until the vacuum reached about 100 Pawhile maintaining the temperature of the copolymer solution at 18±1° C.The distilled solution is collected in a cold trap and monitored byGC-MS until no unreacted monomers, including HFO-1234ze and ethyl vinylether, or solvent were detected. The vacuum pump, agitation andtemperature control is discontinued. Then ZnO was removed off byfiltration. A transparent and colorless copolymer solution was obtained.After that, added Al₂O₃ molecular sieve A202-HF, a UOP product (8.0 wt %of the total polymer weight) or molecular sieve P188, a UOP product (2.0wt % of the total polymer weight) or Al₂O₃ powder (7 wt %) were addedinto the clear copolymer solution and the solution is heated to 87±2° C.for 14-18 hours with 250 rpm agitation. Agitation is then stopped, theglass flask is cooled to room temperature, the Al₂O₃ molecular sieve wasremoved off by filtration, a clear solution was obtained. The solutionwas then condensed to 50-80 wt % solid content.

What is claimed is:
 1. A fluorocopolymer formed by copolymerization ofmonomers comprising: (1) one or more hydrofluoroolefin monomer(s)selected from the group consisting of hydrofluoroethylenes,hydrofluoropropenes, hydrofluorobutenes, hydrofluoropentenes andcombinations thereof, said hydrofluoroolefin being present in thefluorocopolymer in an amount of from about 40 mol % to about 60 mol %based on the total moles of the monomers; (2) one or morechlorofluoroethylene monomers, said chlorofluoroethylene being presentin the fluorocopolymer in and amount of from about 40 mol % to about 60mol % based on the total moles of the monomers, whereby said molar ratioof said hydrofluoroolefin monomers to said chlorofluoroethylene monomersis from about 0.67 to about 1.5; and (3) one or more vinyl ethermonomer(s), wherein at least a portion of said vinyl ether monomer is ahydroxyl group-containing vinyl ether monomer, and wherein saidfluorocopolymer has a hydroxyl value of greater than about
 70. 2. Thefluorocopolymer of claim 1, wherein the one or more chlorofluoroethylenemonomers comprises chlorotrifluoroethylene monomers.
 3. Thefluorocopolymer of claim 1, wherein the one or more hydrofluoroolefinmonomer(s) is selected from hydrofluoropropenes.
 4. The fluorocopolymerof claim 1, wherein the one or more hydrofluoroolefin monomer(s) isselected from 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene,and combinations thereof.
 5. The fluorocopolymer of claim 1, wherein theone or more hydrofluoroolefin monomer(s) is selected from1,3,3,3-tetrafluoropropene.
 6. The fluorocopolymer of claim 5, wherein1,3,3,3-tetrafluoropropene comprises trans-1,3,3,3-tetrafluoropropene.7. A fluorocopolymer formed by copolymerization of monomers comprising:(1) one or more hydrofluoroolefin monomer(s) selected from the groupconsisting of hydrofluoroethylenes, hydrofluoropropenes,hydrofluorobutenes, hydrofluoropentenes and combinations of these, saidhydrofluoroolefin being present in the fluorocopolymer in an amount offrom about 40 mol % to about 60 mol % based on the total moles of themonomers; (2) one or more chlorofluoroethylene monomers, saidchlorofluoroethylene being present in the fluorocopolymer in and amountof from about 40 mol % to about 60 mol % based on the total moles of themonomers, whereby said molar ratio of said hydrofluoropropene monomersto said chlorofluoroethylene monomers is from about 0.67 to about 1.5;(3) one or more vinyl ester monomer(s); and (4) one or more vinyl ethermonomer(s), wherein at least a portion of said vinyl ether monomer is ahydroxyl group-containing vinyl ether monomer, and wherein saidfluorocopolymer has a hydroxyl value of greater than about
 70. 8. Thefluorocopolymer of claim 7, wherein the one or more chlorofluoroethylenemonomers comprises chlorotrifluoroethylene monomers.
 9. Thefluorocopolymer of claim 7, wherein the one or more hydrofluoroolefinmonomer(s) is selected from hydrofluoropropenes.
 10. The fluorocopolymerof claim 9, wherein the one or more hydrofluoroolefin monomer(s) isselected from 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene,and combinations thereof.
 11. The fluorocopolymer of claim 10, whereinthe one or more hydrofluoroolefin monomer(s) is selected from1,3,3,3-tetrafluoropropene.
 12. The fluorocopolymer of claim 11, wherein1,3,3,3-tetrafluoropropene comprises trans-1,3,3,3-tetrafluoropropene.13. A fluorocopolymer formed by copolymerization of: (1) from about 40mol % to about 60 mol % hydrofluoropropene monomers; (2) from about 40mol % to about 60 mol % chlorofluoroethylene monomers, whereby saidmolar ratio of said hydrofluoropropene monomers to saidchlorofluoroethylene monomers is from about 0.67 to about 1.5; (3) fromabout 5 mol % to 45 mol % of vinyl ester, vinyl either ether or amixture thereof, wherein the vinyl ester has the formulaCH₂═CR¹—O(C═O)_(X)R² wherein x is 1, R¹ is a hydrogen or a methyl group,and R² is selected from the group consisting of an unsubstitutedstraight-chain, branched-chain or alicyclic alkyl group having 1 to 12carbon atoms, and wherein the vinyl ether has the formula CH₂═CR³—OR⁴,wherein R³ is a hydrogen or a methyl group, and R⁴ is selected from thegroup consisting of an unsubstituted straight-chain, branched-chain oralicyclic alkyl group having 1 to 12 carbon atoms; and (4) from about 3mol % to about 30 mol % of hydroxyalkyl vinyl ether having the formulaCH₂═CR³—O—R⁵—OH, where R³ is a hydrogen or a methyl group, and R⁵ isselected from the group consisting of a C2 to C12 unsubstitutedstraight-chain, branched-chain or alicyclic alkyl group having from 3 to5 carbons, wherein the mol % are based on the total of the monomers, andwherein said fluorocopolymer has a hydroxyl value of greater than about70.
 14. The fluorocopolymer of claim 13, comprising from about 45 mol %to about 55 mol % of hydrofluoropropene monomers.
 15. Thefluorocopolymer of claim 13, comprising from about 50 mol % ofhydrofluoropropene monomers.
 16. The fluorocopolymer of claim 13,wherein the hydrofluoropropene monomers are selected from the groupconsisting of HFO-1234ze, HFO-1234yf and combinations of these.
 17. Thefluorocopolymer of claim 16, wherein the hydrofluoropropene monomers aretrans-HFO-1234ze.
 18. The fluorocopolymer of claim 13, comprising fromabout 45 mol % to about 55 mol % chlorofluoroethylene monomers.
 19. Thefluorocopolymer of claim 13, wherein the chlorofluoroethylene monomersare CTFE.
 20. The fluorocopolymer of claim 13, comprising from about 10mol % to about 40 mol % of vinyl ester, vinyl ether or a mixturethereof.
 21. The fluorocopolymer of claim 13, comprising from about 20mol % to about 40 mol % of vinyl ester, vinyl ether or a mixturethereof.
 22. A fluorocopolymer composition comprising thefluorocopolymer of claim 13 and further comprising a carrier, whereinthe fluorocopolymer comprises from about 3 mol % to about 20 mol % ofthe hydroxyalkyl vinyl ether, wherein said fluorocopolymer has ahydroxyl value of greater than about 70, wherein the fluorocopolymercomposition has a solids content of from about 70% to about 90% byweight, and wherein the fluorocopolymer composition has a volatileorganic compound content of from about 100 g/l to about 450 g/1.
 23. Afluorocopolymer coating composition comprising: (i) one or morefluorocopolymers formed by the copolymerization of: (1) first monomer(s)consisting essentially of trans-HFO-1234ze in an amount of from about 40mol % to about 60 mol %, (2) second monomer(s) consisting essentially ofCTFE in an amount of from about 20 mol % to about 30 mol %, whereby saidmolar ratio of said trans-HFO-1234ze to said CTFE is from about 1.33 toabout 3, (3) third monomer(s) comprising: A) vinyl ester monomerrepresented by formula CH₂═CR¹—O(C═O)_(X)R² wherein x is 1 and whereinR¹ is either hydrogen or a methyl group and wherein R² is anunsubstituted branched-chain alkyl group having 6 to 8 carbon atomsincluding at least one tertiary or at least one quaternary carbon atom,wherein said vinyl ester monomer is present in an amount of from about 5mol % to about 45 mol %; and B) vinyl ether monomer(s), represented byformula CH₂═CR³—O—R⁴, wherein R³ is either hydrogen or a methyl groupand wherein R⁴ is selected from the group consisting of a substituted orunsubstituted straight-chain or branched-chain alkyl group having 1 to 3carbon atoms, said vinyl ether monomer(s) being present in amounts offrom about 10 mol % to about 40 mol %; and (4) fourth monomer(s)consisting of hydroxyalkyl vinyl ether represented by the formulaCH₂═CR³—O—R⁵—OH, where R³ is either hydrogen or a methyl group and R⁵ isselected from the group consisting of a substituted or unsubstitutedstraight-chain or branched-chain C3 to C5 alkyl, wherein the amount ofsaid fourth monomer is from about 3 mol % to about 30 mol %, wherein themolar percentages of said first through fourth monomers are based on thetotal moles in the fluorocopolymer; and (ii) a carrier comprising one ormore VOC compounds; wherein the fluorocopolymer coating composition hasa solids content of from about 70% to about 90% by weight; and whereinthe coating composition comprises not greater than about 30% by weightof said carrier.
 24. The fluorocopolymer of claim 23, wherein saidfluorocopolymer has a hydroxyl value of greater than about 70.